Disazo dyestuffs



United States Patent 3,197,455 DISAZQ DYESTUFFS Jean-Pierre Jung, Riehen, near Basel, and Guido Schetty, Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland No Drawing. Filed Dec. 10, 1962, Ser. No. 243,620 Claims priority, application Switzerland, Dec. 15, 1961, 14,5'57/61 4 Claims. (Cl. 260-160) The present invention concerns new disazo dyestuffs, processes for the production thereof, processes for the dyeing of fibres containing natural or synthetic polypeptide as well as, as industrial product, the material fast dyed with the aid of these dyestuffs.

It has been found that valuable dyestuffs are obtained by coupling (a) two mols of a diazotised, negatively substituted amine DNH of the benzene series,

(b) with one mol of a coupling component of the Formula I each D is a phenyl radical with from one to two negative substituents as defined below, from zero to maximally four, and preferably two, of which negative substituents in both Ds together are water solubilisin g groups which dissociate acidically in water,

each Y is a phenylene radical which is preferably unsubstituted or is further substituted with from one to two of the substituents chloro, bromo, methyl, ethyl, SO H and COOH, and

A is the CO or preferably the SO radical,

with the proviso that the total number of water-solubilising groups, including -SO H and COOH is at least 1 and maximally 4.

D in Formula II represents a phenyl radical with from one to two negative substituents and which can contain further substituents compatible with an dyestuffs. In this specification and in the appended claims negative substituents in D mean the following substituents: trifiuoromethyl, cyano and, especially those which contain an oxygen atom and the bond of which between the linking atom and the oxygen is semipolar, namely, the nitro, carboxy, lower alkyl-carbonyl, lower alkoxy carbonyl, as well as, in a preferred group of dyestuffs according to the invention, the sulphonyl-containing group of the formula in which R is hydroxyl, phenyl, methylphenyl, chlorophenyl, phenoxy, methylphenoxy, chlorophenoxy, bromophenoxy, chloroacetylaminophenoxy, N-lower alkyl-N- phenyl-amino, phenyl in all the foregoing radicals R containing the same, being either unsubstituted or substituted with SO H or COOH.

Lower alkyl :as used in this specification means alkyl with from lto 5 carbon atoms.

As additional substituents, the phenyl radical of the diazo components D usable according to the invention ice can also contain the following substituents compatible with azo dyestuffs: lower alkyl groups such as methyl, ethyl, nor tert. butyl or tert. amyl; the benzyl, methylbenzyl or chlorobenzyl group; phenyl, lower alkyl phenyl, chloro phenyl, or bromophenyl; lower alkoxy groups such as 'methoxy, ethoxy, or butoxy; the benzyloxy group; phewherein R is phenyl, methylphenyl, chlorophenyl or bromophenyl (or their sodium, potassium or ammonium salts), and either the aforesaid D or Y contain the said group or groups so that the dyestuffs of Formula 11 above contain at least one, especially one to four, and preferably two of said water-solubilising, acidically-dissociating groups, preferably a sulphonic acid group.

Particularly suitable diazo components are aminobenzene sulphonic acids, am-inophenyl sulphones, aminobenzene sulphonic acid N-alkyl-N-phenyl-amides as well as amino diphenylethers wherein all phenyl radicals can be free from or can contain sulphonic acid groups.

The diazotisation is performed in a known way, for example, in mineral acid, aqueous solution with the alkali metal salts of nitrous acid or in concentrated sulphuric acid with nitrosyl sulphuric acid.

The coupling components of the above formula I usable according to the invention are bis-(pyrazolyl-phenylysuL phones which can be coupled in the 4'-position such as, bis[2-, 3- :or 4-(3-methyl-5-amino-pyrazolyl-(1))- phenyl]-sulphone, bis-[3-(3-methyl5'amino pyrazolyl- (l))-4-sulphophenyl] sulphone, bis[4-(3'-methyl-5'- aminopyrazolyl-(1))2-chlorophenyl]-sulphone or bis- [3-(3'-methyl-5-amino pyrazolyl-(l))4-chlorophenylor -4-methylphenyl]-sulphone, bis(pyrazolyl-phenyl)- ketones such as bis-[3- or 4-(3'-methyl-5-amino-pyrazolyl-(l) )-phenyl]-ketone and his [3 (3'-methyl-5'- amino-pyrazolyl-(l') )-chlorophenyl)-ketone. These coupling components are new and they are obtained, for example, by condensing 2 mols of cyanoacetone or cyano acetoneimine by known methods preferably in mineral acid, aqueous solution, with a bis-hydrazine of Formula III NH NHYAYNHNH (III) wherein A and Y have the meanings given in Formulae I and II,

Particularly valuable dyestuffs are obtained on using bispyrazolyl compounds of the Formula I previously mentioned wherein A represents the sulphonyl group S0 and the two benzene rings Y are preferably unsubstituted or are further substituted by halogen such as, chlorine or bromine, low alkyl groups such as methyl or ethyl groups and/ or sulphonic acid or carboxy groups.

The diazotised amine is coupled at a temperature of about 1(l to +50 C. and preferably at +l0 to 25 C. with the bis-pyrazolyl compound of Formula I as defined above, advantageously in an aqueous-acid 4 Further details can be seen from the following examples. Where not otherwise'expressly stated, parts are 9 a medium, while, if desired, gradually buffering the acid with an agent which raises the pH value, e.g. with an alkali metal salt of a low-molecular fatty acid such as given as parts by weight. The temperatures are in degrees sodium acetate and, it necessary, in the presence of centigrade. The relationship of parts by weight to parts organic solvents which are miscible with water such as by volume is as that of grammes to cubic centimeters.

EXAMPLE 1 g -g w wherein M represents the oxo or the imino group, to form a monoazo dyestuti or Formula V GH3COHCN M N=ND V wherein D has the meaning given in Formula II, and condensing two mols of the monoazo dyestufi so obtained, in an acid aqueous medium, with one mol of a bis-hydrazine of Formula 111 to form a disazo dyestuif of Formula II.

The diasazo dyestuifs of Formula 11 produced according to the invention are. isolated in the form of their ammonium or alkali metal salts. As such they are yellow, orange to brown powders. They are excellently suitable for the dyeing and printing of natural and synthetic polypeptide fibres such as leather, silk or, principally, wool as well as of synthetic polyamide and polyurethane fibres such as nylon or Perlon. The dyeings obtained on these A solution of the sodium salt of 26.5 parts of 4-aminodiphenyl-ether-3-sulphonic acid and 6.9 parts of sodium nitrite in 500 parts of Water is added at 05 to parts of concentrated hydrochloric and the amount of ice necessary for cooling. On completion of the diazotisation, the colourless diazo suspension is poured at 0-10" slowly into the solution of 20.4 parts of bis[4-(3'-methyl-5 amino-pyrazolyl-(l'))-phenyl]-sulphone in 500 parts of ethanol while stirring. Coupling occurs immediately and the solution turns yellow. The mineral acid is buttered 0 by the dropwise addition of sodium acetate solution until the reaction solution no longer turns congo paper blue. The reaction mixture is then stirred for several hours at 20-30 until no more diazonium compound can be traced. The disazo dyestuif is precipitated with the aid of 1000 parts of water and 150 parts of sodium chloride, filtered off under suction, washed with 5% sodium chloride solution and dried.

The yellow dyestuif which dissolves well in hot water dyes wool from a neutral to weakly acid bath in the 40 presence of ammonium sulphate in pure, greenish-yellow,

very level shades which are fast to Wet and light.

The bis-[4-(3'-methyl-5-amino-pyrazolyl-(1)) phenyl]-sulphone of MP. 237 used as coupling component is obtained by reacting 1 mol of 4,4'-bis-hydrazino-1,1'-

diphenyl sulphone with 2 mols of cyanoacetone imine in a hydrochloric acid, aqueous medium.

EXAMPLE 2 35.6 parts of B-aminobenzene-l-sulphonic acid N-ethyl- N-4'-sulphophenylamide are dissolved in 800 parts of water with the addition of sodium hydroxide. 6.9 parts of sodium nitrite are added and then 30 parts of concentrated hydrochloric acid are added at 05 and the mix ture is stirred for 1 hour at 0-10". After decomposition of the excess nitrous acid, 20.4 parts of bis-[3-(3-methyl- 5'-amino-pyrazolyl (1')) phenyl] -sulphone are added. The coupling occurs immediately and the suspension turns yellow. The mineral acid is bulfered'by the dropwise addition of sodium acetate solution until the reaction suspension no longer turns 'congo'paper blue and then the mixture is stirred for several hours at 10-20 until no more diazoniurn compound can be traced. The disazo dyestufi which has partly precipitated is completely precipitated with the aid of sodium chloride. form of the'sodium salt and is filtered off, if necessary fibres are usually distinguished by the purity of their greenish-yellow, yellow or orange shades, a good fastness to light and excellent fastness to alkali. They draw onto wool from a neutral to weakly acid bath and the wool dyeings obtained have very good fastness to washing, 7 milling, sea water, chlorine, and rubbing.

Particularly those new disazo dyestufis of Formula II according to the invention wherein D-NH is an o- I aminodiphenyl sulphone radical are preferred because of their excellent fastness to light and excellent fastness in the other above-listed-wet treatments. Those wherein DNH is a m-aminobenzene sulphonylor a m-amino-' benzene carbonyl radical are preferred becauseof their very pure, very greenish-yellow shade, and are therefore very valuable as combination dyestuffs, since they can be combined well with pure blue dyestuffs to give brilliant green shades.

It is in the dissolved and allowed to crystallise from water, and dried.

The dyestufl is a yellow powder which dissolves in hot water with a greenish yellow colour. It dyes wool, silk and synthetic polyamide fibres from a neutral to weakly acid bath in pure, very greenish-yellow shades having very good fastness properties.

The bis[3-(3'-methyl-5-arnino-pyrazolyl-(l)) phenyl1-sulphone of M1. 224 used as coupling component is obtained by reacting 1 mol of 3,3-bis-hydrazino-l,1'-

5 ethanol.

6 ponent of Example 3. The colourless diazo suspension is then poured into the solution of 18;6 parts of bis-[4-(3'- methyl-5-amino-pyrazolyl-(1'))-phenyl}-ketone and parts of concentrated hydrochloric acid in 500 parts of Coupling occurs immediately and the colour turns yellow. The mineral acid is buttered by the dropwise addition of sodium acetate solution until the reaction solution no longer turns congo paper blue and the whole is stirred for several hours at 2025 until no more diazonidiphenyl sulphone with 2 mols of cyanoacetone imine in 10 um o d can b t d, Th partly recipitated a hydrochloric acid, aqueous medium.

EXAMPLE 3 31.3 parts of the sodium salt of 2-amino-l,1-diphenyl sulphone-3'-sulphonic acid are dissolved in 500 parts of water, 6.9 parts of sodium nitrite are added and the solution is added dropwise while stirring at 0-5 to parts disazo dyestuff is completely precipitated with the aid of sodium chloride, filtered off, if necessary dissolved in water and recrystallised and dried in vacuo at 80-85 The dyestutf is a yellow powder which dissolves in hot water with a greenish-yellow colour. It dyes wool at the of concentrated hydrochloric acid and 100 parts of ice. 30 boil from a bath containing ammonium sulphate in level After stirring for 1 hour at 0-5, the excess nitrous acid is decomposed and the colourless diazo suspension is poured into a solution of 20.4 parts of bis-[3-(3'-rnethyl- 5'-amino pyrazolyl-(l'))-phenyl]-sulphone in 500 parts pure greenish-yellow shades which are fast to wet and light.

The bis-[4-(3'-methyl-5'-amino-pyrazolyl-(1')) phen ylJ-ketone of MP. 227 used as coupling component is of ethanol. Coupling occurs immediately and the colour Obtained by reacting 1 mol of 4,4-bis-hydrazino-l,1'-

turns yellow. After adding parts of crystallised sodium acetate, the coupling mixture is stirred for 6 hours at 0-l0, then diluted with 1000 parts of water, 200 parts of sodium chloride are added and the precipitated yellow disazo dyestuff is filtered off under suction. It is washed with a 10% aqueous solution of sodium chloride and dried in vacuo at 8085.

The dyestufi is a yellow powder which dissolves in hot EXAMPLE 4 diphenyl ketone with 2 mols of cyanoacetone imine in a hydrochloric acid aqueous solution.

water. The mixture is stirred for several hours at 0-10,

32.6 parts of 2-amino-4'-methyl1,1-diphenyl disulphimide are diazotised in the same way as the diazo com- 100 parts of sodium chloride are then added, the precipitated dyestufl is filtered ofi and dried.

EXAMPLE 6 31.3 parts of Z-amino-LP-diphenyl sulphone-3'-su1- phonic acid are diazotised as described in Example 3 and coupled at 0-5 withthe solution of 8.2 parts of cyanoacetone imine and parts of concentrated hydrochloric acid in 400 parts of water. After the addition of 50 parts of crystallised sodium acetate, the mixture is stirred for 4 hours at 5-10" whereupon the formation of the monoazo dyestufi' is complete. A freshly prepared hydrochloric acid solution of 13.5 parts" of 3,3'-bis-hydrazino- 1,l'-diphenyl sulphone (produced, e.g. by reducing tetrazotised 3,3-diamino-1,l-diphenyl sulphone with sodium sulphite) and 500 parts of ethanol is then added to the pale yellowish coloured dyestuff solution and the whole is boiled for 1 hour. Condensation to the disazo dyestutf of the above formula occurs while the colour gradually becomes more strongly yellow. The dyestuif solution is then cooled to 20 whereupon the dyestufi already partly precipitates. It is precipitated by the addition of 200 parts of sodium chloride, filtered oliwashed with 10% aqueous sodium chloride solution and dried.

The dyestuif is identical with that according to Example 3.

EXAMPLE 7' 100 parts of previously Well wett ed wool are entered at 50 into a bath containing 1.5 parts of the greenish-yellow dyestufi according to Example 3, 5 parts of ammonium sulphate and 5 parts of sodium sulphate in 3000 parts of water. The bath is brought to the boil within 10 minutes and kept at the boil for minutes. In this time the dyestuif has substantially completely drawn onto the wool. The wool dyeing obtained is extraordinarily pure greenish-yellow, very level and has excellent fastness to wet and light.

Further dyestuffs according to the invention are given in the following Table I which are produced by usingcorresponding amounts of diazo and coupling components according to the methods described in Examples 1 to 6.

Table I Diazo component Shade of wool dyeing Coupling component 4-aminodiphenylether-Ii-sulphonic acid Z-aminohenzene-l-sulphonic acid-N-ethyl-N-( leulphophenyD-amide.

Greenish yellow.

4-amino-4-ehloro-1,1-diphenyl-disulphimide Z-aminobenzene-l-sulphonie acid--- 2-emino-4'-methyl-l,l-diphenyl-disulphimide 3-aminobenzene-1-sulphonic aeid-(4-methyl-3'-sulphophenyD-ester.

2-amino-1,1-diphenylsulphone-3-sulphon.ic acid Z-aminobenzene-l-sulphonic acid-N-ethyl-N-(4'-sulphophenyD-amide.

4-aminobenzeue-1-sulphouic aeid-N-ethyl-N-(y-sulphophenyD-amide.

2-amino-l,1-diphenyl sulphone 2-amlnobenzene-1sulphonic acid-(4-chloroaeetylaminophenyD-ester.

3-amino-G-meghylbenzene-l-sulphonie acld-Nethyl-N- phenylami e. '2-aminobenzene-1-sulphonic acid-(2-methylphenyl)-ester 2-emino-5-ehloroacetylaminobenzene-l-sulphonlc acid (2-- methylphenyD-ester. 3-aminobenzene-1-sulphoule ac1d-N-methyl-N-phenyL amide. 4 amino-4'-methyl-l,l-diphenyl-disulphimide Z-aminobenzene sulphonic acid. V 3-amino-4-methyl-1,1-diphenylsulphone-3 sulphome acid. B-amino-l.1-diphenylsulphone-3-sulphonie acid 2-amino-4'-chloro-l,1-diphenyl-dlsulphlmide 3-amino-4-ehloro-l,l-diphenyl-dlsulphiiuide 2-aminobenzene-1-sulphonie acid- 4-aminobenzene-1-sulphonic acid Q-amin0-1.1-diphenylsulphone-3-sulphomcacid 2-aminobenzene-1-sulphonie aeid-N-ethyl-N-(4-sulphophenyD-amide. z-amino-5-nitrobenzene-1sulphome acid 4-eminobenzene-1-sulphonie acid-Nethyl-N- -sulph0- phenyl)-amide.

bis-[3 (3-ruethyl-5'-am inopyrazolyl-(1')) -4-chlorophenyl]- sul phone.

2-anziino-1,1-dlphenylsulphone-3sulphonlo Mid n V 4-amino-4-methyl-1,1'-dlphenyl-disnlnhimMp 4-amlnobenzene-1-sulphonic acid.

Yellow.

Greenish yellow.

Do. Do. Yellow. Greenish yellow.

Do. Do. Do. Yellow.

Orange. Yellow.

Do. Do.

Yellow. 7 Greentsh yellow. D 0. I

Talile I-Continued No. Diazo component Coupling component Shade of wool dyeing 35 2-amino-1,1-diphenylsulphone-S'sulphonie acid Meg-(k3 methyl-5-amino-pyrazolyl- (l'))-2-chlorophenyl]- Yellow.

5 p one. 36 A-arnigiol-methyl-1,1-diphenylsulphone-3-sulphonic do Do.

aoi 37 3-mginolienzlgng-l-sulphonic acid-N-ethyl-N-(y-sulphodo Greenlsh yellow.

p eny a e. 38 3-amino-6-methyl-l,l-diphenylsulphone-3-sulphonic acid bis-3(3-methy1-5-amlno-pyrazolyl-(1))phenyH-sul- Do.

p one. 39 2-amino-5-nitrobenzene-l-sulphonie acid do Orange. 40 2-amino-5ehloroacetylamino-benzene-l-sulphonie acid do Yellow. 41 4- (4 ,6-dichloro-l ,3,5-trlazinylamlno)-2-aminohenzened 0 Do.

1-sulphonie acid 3-aminobenzene-1-sulphonlc acid-.- Greenish-yellow. 4-aminobenzene-1-sulph0nic acid- Do. 4-amino-diphenyl ether-S-sulphordo acid D0. 2-amino-diphenyl ether-4-su1phonio acid Do. 2-amlno-l,1-diphenyl sulphone-3-su.lphonlc acid- Yellow. 2-am nobenzene-1-sulphonic acid-N-cthyl-N-(4-sulphoo.

phenyD-amide 2-aminobenzene-l-carboxyllo acid bls-I3-(3-methy1-5-arnlnopyrazolyl-(l))-4eulpho- Do.

phenyl1-sulphone. 2amino-4-methyl-1-1-diphenyl-disulphlmide. Do. l-amino-benzene-25-disulphonic acid bis-g3-(3fineflh3g-5amino-pyrazolyl-(1))-2-5-dibromo- Greenlsh yellow.

p eny -s one. 2-amlno-1,1-diphenylsuJphone3-sulphonic acid bis-[f-(h3-met yl5-am.tnopyrazolyl-(1))-4-ch1orophenyl]- Yellow.

511 p one. Z-amino-l,l-diphenylsulphone-ssulphonic acid bis-1%gi methyl-5-aminopyrazolyl-(1'))4brornophenyl} Do.

su p one. Z-amino-4'-chloro-l-1'-diphenylsulphone-3'-sulphonic acid. bis-[3-3-methyl-5-amino-pyrazo1yl(1))-phenyl]-sulphone. D0. 54 2-amino-4-methyl1-l-diphenylsulphone-3-sulphonlc acid Do. is (in bis-[3-(3'-methyl-5-amlnopyrazolyl-(l)) A-methyl- Do.

phenyH-sulphone. 56 Q-amino-benzene-l-sulphonic acid-N-ethyl-N-4-sulphodo Do.

phenylamide. 57 do bis4?-gif-methyl-amlno-pyrazolyl-(1'))4 -ethylphenyl1- Do.

su p one. 58 domino-1,l-dlphenylether-3-sulphonic aci do Greenish yellow. fi do bis-[2-(3'-methy1-5'-arnlno-pymzoly1-(1))-4-carboxy- Do.

phenyH-sulphone. 6O 2-aminobenzene-lsnlphonic acid-4'-amy1phenyl ester bisglz3-methy1-5-amino-pyrazolyl-(1))-4-sulphopl1enyl]- Yellow.

5 p 10116. 61 l- 3-amino-1,1-diphenylketone bis-[3-(3-methyl-oamino pyrazolyl-(l'))-4-sulpho- Greenlsh yellow.

phenyll-disulphlmlde. 62 do bis-[3'(3-methyl-5-aminopyrazolyl'(1))-4-sulphophenyl]- Do.

What is claimed is: 1. A disazo dyestufi of the formula sulphone.

roacetylamino, 4,6 dichloro-s-triazinyl-(Z)amino, and

lower alkyl, each Y is a phenyl one radical with from one to two substituents selected from the group consisting of hydrogen, chloro, bromo, methyl ethyl,

COOH, and A is a member selected from the group consisting of CO and -SO the total number of said water-solubilizing groups being at least 1 and maximally 4.

2. A disazo dyestuif of the formula 3. A disazo dyestuff of the formula HOaS N N N 4. A disazo dyestufi' of the formula HZN A -NH, 2

HOaS- SOsH References Cited by the Examiner 15 FOREIGN PATENTS 8 44 Switzerland. 8/44 Switzerland. 7/ 44 Switzerland.

CHARLES B. PARKER, Primary Examiner. 

1. A DISAZO DYESTUFF OF THE FORMULA DI((3-(H3C-),4-(D-N=N-),5-(H2N-)-PYRAZOL-1-YL)-Y)-A WHEREIN EACH D IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF CARBOXYPHENYL, SULFOPHENYL, PHENOXYPHENYL, PHENSULFONYLPHENYL, PHENOXYSULFONYLPHENYL, N-PHENYLN-LOWER ALKYLSULFAMYL-PHENYL, N-PHENYLSULFONYL-SULFAMYLPHENYL, AND BENZOYLPHENYL, BOTH D''S TOGETHER CONTAINING FROM 0 TO MAXIMALLY 4 WATER-SOLUBILIZING GROUPS SELECTED FROM THE CLASS CONSISTING OF -COOH AND -SO2H, THE PHENYL RING IN D WHICH IS ATTACHED TO THE ADJACENT AZO BRIDGE, BEING FURTHER SUBSTITUTED BY A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, NITRO, CHLORO, CHLOROACETYLAMINO, 4,6-DICHLORO-SITRIAZINYL-(2)-AMINO, AND LOWER ALKYL, EACH Y IS A PHENYL ENE RADICAL WITH FROM ONE TO TWO SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, CHLORO, BROMO, METHYL ETHYL, -SO3H AND -COOH, AND A IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF -CO AND -SO2-, THE TOTAL NUMBER OF SAID WATER-SOLUBILIZING GROUPS BEING AT LEAST 1 AND MAXIMALLY
 4. 